Patent GB-557294-A (GB)
Title: Improvements in photographic sensitizing dyes and in silver salt emulsions containing them
IPC: C09B23/10
Filed: 1942-05-11
Abstract: 557,294. Dyes; sensitizing photographic emulsions. KODAK, Ltd. May 11, 1942, No. 6342. Convention date, Aug. 9, 1941. [Class 2 (iii)] [Also in Group XX] A dye of the formula shown in Fig. 3 is prepared by treating a quaternary salt of the formula shown in Fig. 2 with an alkali metal selenide, n being 1 or 2, L a methine group (including an alkyl substituted methine group), Q sulphur or arylimino, R and R<SP>1</SP> the same or different alkyl or aryl group, and Z the non- metallic atoms necessary to complete a 5- or 6-membered heterocyclic nucleus in the presence of a liquid diluent. The heterocyclic nucleus may be an oxazole nucleus (e.g. 4-methyloxazole, 4-phenyloxazole, benzoxazole, or naphthoxazole), a thiazole nucleus (e.g. 4-methylthiazole, 4-phenylthiazole, benzthiazole, 5-chlorobenzthiazole, and naphthathiazole), a selenazole nucleus (4-methylselenazole, 4-phenylselenazole, or benzselenazole), a thiazoline nucleus, a pyridine nucleus, or a quinoline nucleus. The alkyl group may be a substituted alkyl group, e.g. methyl, ethyl, n-butyl, isoamyl, benzyl, allyl, or #-ethoxyethyl. The diluent may be a lower aliphatic alcohol which may have from 1 to 4 carbon atoms. 3-ethyl-5-(3<SP>1</SP>-ethyl-2<SP>1</SP>- benzthiazolylidene) - 2 - selena - 2:4 - thiazoledione is prepared by reacting together 5-(31-ethyl-21- benzthiazolylidene) - 2 - methylmercapto - 4 - thiazolone ethiodide and sodium selenide in ethyl alcohol at 20-25C. 3-ethyl-5-[(3<SP>1</SP>-ethyl- 2<SP>1</SP>- benzoxazolylidene) - ethylidene] - 2 - selena - 2:4 - thinzoledione, 3 - ethyl - 5 - [(1<SP>1</SP> - ethyl - 2<SP>1</SP> - # - naphthathiazolylidene) - ethylidene] - 2 selena - 2:4 - thiazoledione, 3 - ethyl - 5 - [(3<SP>1</SP> - ethyl - 21 - benzthiazolylidene) - ethylidene] - 2 selena - 2:4 thiazoledione, 3 - - ethyl - 5 - [(1<SP>1</SP> - ethyl - 2 qttinolylidene) - ethylidene - 2 - selena - 2:4 - thiazoledione, 3 - ethyl - 5 - [(31 - ethyl - 2<SP>1</SP> - benzthiazolylidene) - isopropyli - dene] - 2 - selena - 2:4 - thiazoledione, 3 - ethyl - 5 - [(3<SP>1</SP> - ethyl - 2<SP>1</SP> - benzthiazolylidene) - α - ethylethylidene] - 2 - selena - 2:4 - - thiazoledione, 3 - ethyl - 5 - [(1 - ethyl - 2 - # - naphthathiazolylidene) - α - ethylethylidene] - 2 - selena - 2:4 - thiazoledione, 5 - (3<SP>1</SP> - ethyl - 2<SP>1</SP> - benzoxazolyli - dene) - ethylidene - 3 - phenyl - 2 - selena - 2:4 - thiazoledione, 5 - [3<SP>1</SP> ethyl - 2<SP>1</SP> - benzoxazolyli - dene) - 1:3 - diphenyl - 2 - selenahydantoin, 3 - ethyl - 5 - [(3<SP>1</SP> - ethyl - 21 - benzoxazolylidene) - ethylidene] 1 - phenyl - 2 - selenahydantoin, 3 - ethyl - 5 - [(3<SP>1</SP> phenyl - 2<SP>1</SP> - benzthiazolyli - dene] - ethylidene] - 2 - selena - 2:4 - thiazoledione, and 3 - ethyl - 5 - [(3<SP>1</SP>:4<SP>1</SP> - trimethylene - 2 - benzthiazolylidene) - ethylidene] - 2 - selena - 2:4 - thiazoledione are similarly prepared. 5 - (3<SP>1</SP> - ethyl - 2<SP>1</SP> - benzoxazolylidene) - ethylidene - 2 - - methylmereapto - 4 - thiazoline phenyl p - toluenesulphonate is prepared by heating together 5 - (3<SP>1</SP> - ethyl - 2<SP>1</SP> - benzoxazolylidene) - ethylidene - 3 - phenylohodanine and methyl p-toluenesulphonate. 5 - [(3<SP>1</SP> - ethyl - 2<SP>1</SP> - benzoxazolylidene) - ethyli - dene] - 2 - methylmercapto - 1 - phenyl - 4 - imidazolone pheniodide is prepared by heating together 5 - [(3<SP>1</SP> - ethyl - 2<SP>1</SP> - benzoxazolylidene) - ethylidene] - 1:3 - diphenyl - 2 - thiohydantoin and methyl p-toluenesulphonate in nitrobenzene and adding aqueous potassium iodide to the reaction mixture diluted with acetone. 5 - (3<SP>1</SP> - ethyl - 2<SP>1</SP> - benzthiazolylidene) - 2 - methylmercapto - 4 - thiazolone ethiodide is prepared by heating together 3 - ethyl - 5 - (3 - ethyl - 2 - benzthiazolylidene) - rhodanine and methyl p - toluenesulphonate in nitrobenzene, diluting with acetone, and adding potassium iodide. 5 - [3<SP>1</SP> - ethyl - 2<SP>1</SP> - benzoxazolylidene) - ethyli - dene] - 2 methylmercapto - 4 - thiazolone - etho - ethylsulphate is prepared by heating together 3 - ethyl - 5 - [(3 - ethyl - 2 - benzoxazolylidene) - ethylidene] - rhodanine and diethyl sulphate. 5 - [(1<SP>1</SP> - ethyl - 2<SP>1</SP> - # - naphthathiazolylidene) - ethylidene] - 2 - methylmercapto - 4 - thiazolone ethyl - p - toluenesulphonate, 5 - [(3<SP>1</SP> - ethyl - 2<SP>1</SP> - benzthiazolylidene) - ethylidene] - 2 - methyl - mereapto - 4 - thiazolone ethiodide, 5 - [(1<SP>1</SP> - ethyl - 2<SP>1</SP> - quinolylidene) - ethylidene] - 2 - methylmercapto - 4 - thiazolone ethiodide, 5 -[(3<SP>1</SP> - ethyl - 21 - benzthiazolylidene) - isopropylidene] - 2 - methylmercapto - 4 - thiazolone ethiodide, 5 - [3<SP>1</SP> - ethyl - 2<SP>1</SP> - benzthiazolylidene) - α - ethylethylidene] - 2 - methylmercapto - 4 - thiazo - lone ethiodide, 5 - [(1<SP>1</SP> - ethyl - 2<SP>1</SP> - # - naphtha - thiazolylidene) - α - ethylethylidene] - 2 - methyl - mereapto - 4 - thiazolone etho - p - toluene sulphonate, and 5 - [3<SP>1</SP> - ethyl - 2<SP>1</SP> - benzoxazolyli - dene) - ethylidene) - 2 - methylmercapto - 1 - phenylimidazolone ethiodide are similarly prepared. The dyes may be used as sensitizers for photographic silver halide emulsions, and may be incorporated either by addition to the finished washed emulsion or by bathing a coated plate or film. Sensitizing data are given. Specifications 450,958, 487,051, 551,331, 551,824 and 552,309 are referred to.